Polymer including polymerizable triptycene derivative compound as component

ABSTRACT

It is an objective of the present invention to provide a polymer compound as constituent component a polymerizable triptycene derivative and that has a structure in which three benzene rings arranged at the axis formed by barrelene of the triptycene skeleton can rotate evenly and that has hydrophilicity imparted to it as compared to any of the prior art triptycene derivatives and is thus highly useful in functional materials. 
     The above objective is achieved by the polymerizable triptycene derivative and a polymer compound as constituent component thereof having substituents with an unsaturated bonding functional group at position 9 and/or position 10 of the triptycene skeleton, the polymerizable triptycene derivative having two carboxyl groups and the polymerizable triptycene derivative having one carboxyl group and one amino group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is the US National Stage of International Patent Application No.PCT/JP2019/003546, filed Feb. 1, 2019, which in turn claims the benefitof priority to Japanese Patent Application No. 2018-17415, filed Feb. 2,2018, the disclosure of which is incorporated herein by reference in itsentirety.

TECHNICAL FIELD

The present invention relates to a polymer compound containing atriptycene derivative having a substituted triptycene structure asconstituent component.

BACKGROUND ART

A polymer compound can be obtained by polymerization of one orcombination of two or more of polymerizable compounds such as(meth)acrylic acids and their derivatives as monomer components or bypolycondensation of compounds having a dicarboxylic acid or compoundshaving an amino group and a carboxylic group within the molecules.

The characteristics of the polymer compound can vary widely depending onthe monomer compounds used as constituent materials or theircombinations. Hence, it is necessary to take into consideration suchcombinations of monomer compounds used as constituent materials orprovision of novel monomer compounds for use as constituent materials inorder to obtain polymer compounds having new characteristics or polymercompounds having some of their known characteristics improved. Toprovide novel monomer compounds, known compounds may be chemicallymodified at specific sites or polymerizable functional groups may beadded.

Triptycene is an aromatic hydrocarbon having a paddle wheel-likestructure in which three benzene rings are arranged in a manner similarto paddles of a paddle wheel to give D_(3h) symmetry. Because of such astructure, application of triptycene in various functional materials hasbeen contemplated. Several triptycene derivatives that have a triptycenestructure (skeleton) are also known.

Among known such compounds are, for example, compounds formed by ringfusion of triptycene skeleton with further other ring structures (SeePatent Document 1 below, the disclosure of which is incorporated hereinby reference in its entirety), optically active triptycene derivativesobtained by asymmetric acylation with enzymes (See Patent Document 2below, the disclosure of which is incorporated herein by reference inits entirety), and optically active triptycene derivatives obtained byreacting a mixture of optical isomers of a triptycene derivative havinghydrolyzable functional groups with a hydrolase capable of asymmetrichydrolysis (See Patent Document 3 below, the disclosure of which isincorporated herein by reference in its entirety).

Also known are a photoresist substrate and a photoresist composition inwhich a triptycene derivative with a specific structure are oriented(See Patent Document 4 below, the disclosure of which is incorporatedherein by reference in its entirety); a triptycene ring-containingliquid crystal compound that exhibits a good compatibility with otherliquid crystal compounds, has a small phase shift or a small chromaticdispersion of optical anisotropy, and has polymerizability (See PatentDocument 5 below, the disclosure of which is incorporated herein byreference in its entirety); a triptycene group-containing polymerelectroluminescence material having, optionally substituted, vinylenegroup, ethynylene group, arylene group, heteroarylene group andspirobifluorene group (See Patent Document 6 below, the disclosure ofwhich is incorporated herein by reference in its entirety); atriptycene-containing compound that is one of compounds having apolymerizable group and a 1,4-dimethylenecyclohexane backbone, and thathas a liquid crystal phase and exhibits a good compatibility with otherliquid crystal compounds and organic solvents (See Patent Document 7below, the disclosure of which is incorporated herein by reference inits entirety); and a triptycene-containing compound that is one ofliquid crystal display element compounds that are composed of aphotopolymerizable monomer and/or oligomer selected from a polyimideconsisting of a diamine and a tetracarboxylic acid dianhydride or apolyamic acid derivative, a precursor of the polyimide (See PatentDocument 8 below, the disclosure of which is incorporated herein byreference in its entirety).

Further known is a triptycene derivative having a structure consistingof a barrelene having a plurality of unsaturated polymerizablefunctional groups attached thereto, including a triple bond-containingfunctional group and a double bond-containing functional group (SeePatent Document 9 below, the disclosure of which is incorporated hereinby reference in its entirety).

PRIOR ART DOCUMENT Patent Document

-   Patent Document 1: JP 2011-207792 A-   Patent Document 2: JP 2013-223458 A-   Patent Document 3: JP 2006-187225 A-   Patent Document 4: JP 2008-308433 A-   Patent Document 5: JP 2006-111571 A-   Patent Document 6: JP 2002-539286 A-   Patent Document 7: JP 2011-246365 A-   Patent Document 8: JP 2014-178712 A-   Patent Document 9: JP 2008-075047 A

SUMMARY OF INVENTION Technical Problem

Because most of the prior art triptycene derivatives have a structure inwhich a polymerizable group for forming a polymer extension chain hasbeen incorporated into an aromatic ring of the triptycene skeleton, itis likely that the rotation of the polymer about an axis formed bybarrelenes each having fused three benzene rings is hindered. On theother hand, such a rotation is less likely to be hindered in thetriptycene derivative as described in Patent Document 9 sinceunsaturated polymerizable functional groups are at positions 9 and 10 ofthe triptycene.

However, the hydrophobic nature of alkenyl and alkynyl groups used asthe unsaturated polymerizable functional groups in the triptycenederivative as described in Patent Document 9, as well as hydrophobicnature of triptycene itself, makes the overall triptycene derivative asdescribed in Patent Document 9 hydrophobic. Because of thischaracteristic, the triptycene derivative as described in PatentDocument 9 has limited applications in compositions for use asfunctional materials and is thus less useful.

There is no known the polymerizable triptycene derivatives or thepolymer compounds containing as constituent component the polymerizabletriptycene derivatives that can solve the problems of theabove-described prior art.

Hence, it is an objective of the present invention to provide a novelpolymer compound containing as constituent component a polymerizabletriptycene derivative that has a structure permitting even rotation ofthe three benzene rings arranged about the axis formed by barrelenes ofthe triptycene backbone and that has hydrophilicity imparted to it ascompared to any of the prior art triptycene derivatives and is thushighly useful in functional materials.

Solution to Problem

In an effort to provide the above-described novel polymerizabletriptycene derivatives, the present inventors have focused on the typeand attached positions of polymerizable functional groups involved inthe polymerization reaction. The present inventors have postulated thatin order for the three benzene rings to rotate evenly, it is desirablethat the three benzene rings rotate about the barrelene to which theyare attached. The present inventors have further postulated that apolymerizable triptycene derivative having compatibility with otherhydrophilic compounds can be provided by selecting hydrophilicfunctional groups as polymerizable functional groups to be introduced.

Based on the above-described considerations, the present inventors haveconducted extensive studies and after many trials and failures, havesucceeded in producing a compound that has hydrophilic polymerizablefunctional groups at position 9 and/or position 10 of the triptyceneskeleton. This compound is a polymerizable triptycene derivative havinga structure that permits even rotation of the three benzene ringsarranged about the axis formed by barrelene in the triptycene skeletonand has hydrophilicity imparted to it as compared to any of the priorart polymerizable triptycene derivatives. Thus, the compound can serveas a highly useful functional material. A patent application has beenfiled for a part of the novel polymerizable triptycene derivativescompleted in this manner as Patent Application JP 2016-152953.

The present inventors have succeeded in producing a polymer compoundwith increased compatibility with the other compound capable ofcopolymerizing and forming a good hydrogel by using the polymerizabletriptycene derivative having (meth)acryloyl oxyalkyl group at position 9and/or position 10 of the triptycene skeleton. These findings andsuccessful examples have ultimately led to the completion of the presentinvention.

According to one embodiment of the present invention, there is provideda polymer compound containing as constituent component:

a polymerizable triptycene derivative represented by the followinggeneral formula (1), and

(whereinR₁ to R₄ are each independently a substituent selected from the groupconsisting of hydrogen atom, alkyl group, cycloalkyl group, heterocyclicgroup, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group,alkylthio group, arylether group, arylthioether group, aryl group,heteroaryl group, halogen atom, carbonyl group, carboxyl group,oxycarbonyl group, carbamoyl group, amino group, phosphineoxide group,and silyl group, with the proviso that adjacent substituents maytogether form a ring; one of X and Y is a substituent represented by thefollowing general formula (2):

(wherein n is an integer of 1 to 5; and R₅ shows hydrogen atom or methylgroup.)and the other of X and Y is a substituent selected from the groupconsisting of the substituents represented by the general formula (2),hydrogen atom and halogen atom, and protected or unprotected hydroxylgroup, hydroxylalkyl group, carboxyl group, carboxylalkyl group, aminogroup, aminoalkyl group, aminocarbonyl group, aminocarbonylalkyl group,alkoxy group, alkoxyalkyl group, alkoxycarbonyl group,alkoxycarbonylalkyl group, formyl group, formylalkyl group, and alkylgroup.)a compound capable of copolymerizing with the polymerizable triptycenederivative.

Preferably, the other of X and Y is a substituent selected from thegroup consisting of the substituents represented by the followinggeneral formula (3):

(wherein n is an integer of 1 to 5; and R₆ is a substituent selectedfrom the group consisting of hydrogen atom and alkyl group having anyone of carbons 1 to 3),the substituents represented by the following general formula (4):—(CH₂)_(n)—NHR₇  (4)(wherein n is an integer of 1 to 5; and R₇ is a substituent selectedfrom the group consisting of hydrogen atom and a carbamate protectivegroup), andthe substituents represented by the following general formula (5):—(CH₂)_(n)—OH  (5)(wherein n is an integer of 1 to 5).

Preferably, the compound capable of copolymerizing with thepolymerizable triptycene derivative is at least one hydrophiliccompound.

Advantageous Effects of Invention

Polymerizable triptycene derivatives used in polymer compounds in oneembodiment of the present invention have a structure in whichpolymerizable functional groups are attached to carbons of barrelene,which forms a main skeleton of triptycene, such that each of the threebenzene rings in the triptycene structure can rotate evenly about anaxis formed by the barrelene. Furthermore, the polymerizable triptycenederivatives are compatible with not only hydrophobic compounds but alsowith hydrophilic compounds due to introducing functional groups havinghydrophilicity. Thus, the polymer compound in one embodiment of thepresent invention can be a polymer compound with various functionsdifferent from conventional compounds. In particular, the polymercompound in one embodiment of the present invention can be used toproduce hydrogels swollen by hydration, which were not achieved by anyof prior art techniques.

Furthermore, since the three benzene rings in the triptycene structurein the polymer compound in one embodiment of the present invention canrotate evenly about the axis formed by barrelene, when a material isencapsulated within the polymer compound, it is expected to control therate and the extent of diffusion of the encapsulated material releasedfrom the polymer compound.

DESCRIPTION OF EMBODIMENTS

While polymer compounds containing as constituent componentpolymerizable triptycene derivatives in one embodiment of the presentinvention will now be described in further details, the technical scopeof the present invention is not limited to what is described in thissection; rather, the present invention may take various other forms tothe extent that its objectives are achieved.

The polymer compounds in one embodiment of the present invention arecontained as constituent component: a polymerizable triptycenederivative and a compound capable of copolymerizing with thepolymerizable triptycene derivative.

The polymerizable triptycene derivatives are represented by thefollowing general formula (1).

In the general formula (1), R₁ to R₄ are each independently selectedfrom the group consisting of hydrogen atom, alkyl group, cycloalkylgroup, heterocyclic group, alkenyl group, cycloalkenyl group, alkynylgroup, alkoxy group, alkylthio group, arylether group, arylthioethergroup, aryl group, heteroaryl group, halogen atom, carbonyl group,carboxyl group, oxycarbonyl group, carbamoyl group, amino group,phosphineoxide group, and silyl group. Any adjacent substituents of R₁to R₄ may together form a ring.

In the general formula (1), one of X and Y is a substituent representedby the following general formula (2):

In the general formula (2), n is an integer of 1 to 5; and R₅ showshydrogen atom or methyl group.

In the general formula (1), one of X and Y is a substituent representedby the general formula (2) and the other substituent is a substituentselected from the group consisting of the substituents represented bythe general formula (2), hydrogen atom and halogen atom, and protectedor unprotected hydroxyl group, hydroxylalkyl group, carboxyl group,carboxylalkyl group, amino group, aminoalkyl group, aminocarbonyl group,aminocarbonylalkyl group, alkoxy group, alkoxyalkyl group,alkoxycarbonyl group, alkoxycarbonylalkyl group, formyl group,formylalkyl group, and alkyl group. As used herein, the term “protectedsubstituent” is not particularly limited as long as referring to anysubstituent having any protective group.

The other substituent in the general formula (1) is preferably any ofsubstituents represented by the general formula (2), substituentsrepresented by the general formula (3), substituents represented by thegeneral formula (4) or substituents represented by the general formula(5) as described below.

In the general formula (3), n is an integer of 1 to 5; and R₆ is asubstituent selected from the group consisting of hydrogen atom andalkyl group having any one of carbons 1 to 3.—(CH₂)_(n)—NHR₇  (4)

In the general formula (4), n is an integer of 1 to 5; and R₇ is asubstituent selected from the group consisting of hydrogen atom and acarbamate protective group.—(CH₂)_(n)—OH  (5)

In the general formula (5), n is an integer of 1 to 5.

Specific embodiments of the polymerizable triptycene derivativesrepresented by the general formula (1) include, but are not limited to,polymerizable triptycene derivatives in which X and Y are eachindependently a substituent shown in Table 1 below. In cases where bothX and Y are substituents represented by the general formula (2) as incompound E, they may be an identical substituent or they may besubstituents that differ from each other.

TABLE 1 compound X Y A general formula (2) hydrogen atom B generalformula (2) general formula (3) C general formula (2) general formula(4) D general formula (2) general formula (5) E general formula (2)general formula (2)

In any of the polymerizable triptycene derivatives shown in Table 1, R₁to R₄ may be all different substituents, or two, three, or all four ofthem may be an identical substituent.

While the substituent exemplified for R₁ to R₇ may be not particularlylimited as long as any substituent that has a commonly known meaning,for example, it may be a substituent as exemplified below. In addition,the substituent exemplified for R₁ to R₇ may bear a further substituent.Examples of the further substituent include, but are not particularlylimited to, alkyl group, cycloalkyl group, aryl group and heteroarylgroup.

Examples of the alkyl group include, but are not limited to, saturatedaliphatic hydrocarbon groups, such as methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, sec-butyl group, andtert-butyl group. While the alkyl group may have any number of carbons,it preferably has for example from 1 to 20, more preferably from 1 to 8,and still more preferably from 1 to 3 carbons. Examples of the alkylgroup bearing a substituent include, but are not limited to,hydroxyalkyl group, aminoalkyl group, carboxyalkyl group, andformylalkyl group.

Examples of the cycloalkyl group include, but are not limited to,saturated alicyclic hydrocarbon groups, such as cyclopropyl group,cyclohexyl group, norbornyl group, and adamantyl group. While thecycloalkyl group may have any number of carbons, it preferably has from3 to 20 carbons.

Examples of the heterocyclic group include, but are not limited to,alicyclic rings that contain an atom other than carbon atom, such asnitrogen and sulfur atom, including, for example, pyran ring, piperidinering, cyclic amide. While the heterocyclic group may have any number ofcarbons, it preferably has from 2 to 20 carbons.

Examples of the alkenyl include, but are not limited to, unsaturatedaliphatic hydrocarbon groups having a double bond, such as vinyl group,allyl group, and butadienyl group. While the alkenyl group may have anynumber of carbons, it preferably has from 2 to 20 carbons.

Examples of the cycloalkenyl group include, but are not limited to,unsaturated alicyclic hydrocarbon groups having a double bond, such ascyclopentenyl group, cyclopentadienyl group, and cyclohexenyl group.

Examples of the alkynyl group include, but are not limited to,unsaturated aliphatic hydrocarbon groups having a triple bond, such asethynyl group. While the alkynyl group may have any number of carbons,it preferably has from 2 to 20 carbons.

Examples of the alkoxy group include, but are not limited to, functionalgroups with an aliphatic hydrocarbon group attached via an etherlinkage, including, for example, methoxy group, ethoxy group, andpropoxy group. While the alkoxy group may have any number of carbons, itpreferably has from 1 to 20 carbons. Examples of the alkoxy groupbearing a substituent include, but are not limited to, alkoxyalkylgroup, alkoxycarbonyl group, and alkoxycarbonylalkyl group.

Examples of the alkylthio group include, but are not limited to,functional groups in which the oxygen atom of their ether bond in alkoxygroups is replaced with a sulfur atom. While the alkylthio group mayhave any number of carbons, it preferably has from 1 to 20 carbons.

Examples of the arylether group include, but are not limited to,functional groups having an aromatic hydrocarbon group attached via anether linkage, such as phenoxy group. While the arylether group may haveany number of carbons, it preferably has from 6 to 40 carbons.

Examples of the alkylthioether group include, but are not limited to,functional groups in which the oxygen atom of their ether bond inarylether groups is replaced with a sulfur atom. While the arylthioethergroup may have any number of carbons, it preferably has from 6 to 40carbons.

Examples of the aryl group include, but are not limited to, aromatichydrocarbons, such as phenyl group, naphthyl group, biphenyl group,anthracenyl group, phenanthryl group, terphenyl group, and pyrenylgroup. While the aryl group may have any number of carbons, itpreferably has from 6 to 40 carbons.

Examples of the heteroaryl group include, but are not limited to,5-membered cyclic aromatic groups with their rings containing one atomother than carbon, such as furanyl group, thiophenyl group, benzofuranylgroup and dibenzofuranyl group, and 6-membered cyclic aromatic groupswith their rings containing one or more atoms other than carbon, such aspyridyl group and quinolynyl group. While the heteroaryl group may haveany number of carbons, it preferably has from 2 to 30 carbons.

Examples of halogen atom include, but are not limited to, fluorine,chlorine, bromine, and iodine.

Each of the carbonyl group, carboxyl group, oxycarbonyl group, carbamoylgroup, amino group, formyl group, and phosphine oxide group may bear asubstituent, which in turn may bear a further substituent. Examples ofthe amino group bearing a substituent include, but are not limited to,aminocarbonyl group, and aminocarbonylalkyl group.

Examples of the silyl group include, but are not limited to, functionalgroups having a silicon atom bonded to them, such as trimethylsilylgroup. While the silyl group may have any number of carbons, itpreferably has from 3 to 20 carbons. While the silyl may have any numberof silicons, it preferably has from 1 to 6 silicons.

Any adjacent substituents of the substituents represented by R₁ to R₄,that is, R₁ and R₂, R₂ and R₃, and/or R₃ and R₄ may together form a ring(i.e., fused ring). In other words, the fused ring is formed by anyadjacent two substituents selected from R₁ to R₄ (e.g., R₁ and R₂) thatare bound together to form a conjugated or unconjugated fused ring.Examples of the constituent elements involved in the formation of afused ring include, but are particularly not limited to, carbon atom,nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, and siliconatom. The substituents represented by R₁ to R₄ may be further fused withanother ring.

Examples of the carbamate protective group include, but are not limitedto, carbamate protective groups such as tert-butoxycarbonyl group,benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group,2,2,2-trichloroethoxycarbonyl group, and allyloxycarbonyl group.

More specific embodiments of the polymerizable triptycene derivativesrepresented by the general formula (1) include, but are not limited to,for example, compounds of the following formulas (6), (7), (8), (9),(10), (11) and (12), where Me in the formula represents methyl group:

While the polymerizable triptycene derivative of the present inventionmay be produced by any method that is not particularly limited, it maybe produced for example by using any of the methods described later inExamples or by modifying these methods as desired to obtain desiredpolymerizable triptycene derivatives.

One embodiment of the production method of a polymerizable triptycenederivative of the general formula (1) includes, but not limited to, amethod including: subjecting 9-halogen anthracene or 9,10-dihalogenanthracene and an acetal compound having a vinyl group to Heck couplingreaction and hydrolysis; subjecting the resulting reaction product andbenzyne to Diels-Alder reaction and, optionally, to a reaction formodifying substituents born by benzyne; subjecting the resultingreaction product to reduction with a metal hydride; and subjecting theresulting reaction product to a reaction with a halogenated(meth)acryloyl to obtain a triptycene derivative having a (meth)acryloyloxyalkyl group as a polymerizable triptycene derivative of the generalformula (1).

Another embodiment of the production method of a polymerizabletriptycene derivative of the general formula (1) includes, but notlimited to, a method including: subjecting 9-halogen anthracene or9,10-dihalogen anthracene and an acetal compound having a vinyl group toa Heck coupling reaction and hydrolysis; subjecting the resultingreaction product and benzyne to a Diels-Alder reaction and, optionally,to a reaction for modifying substituents born by benzyne; and subjectingthe resulting reaction product to an alkali treatment and an acidtreatment to obtain a polymerizable triptycene derivative of the generalformula (1) in which at least one of X or Y is a substituent representedby the general formula (3).

Another embodiment of the production method of a polymerizabletriptycene derivative of the general formula (1) includes, but notlimited to, a method including: subjecting 9-halogen anthracene oranthracene and an amide compound to a Vilsmeier-Haack reaction;subjecting the resulting reaction product and a primary amine having acarbamate protective group to an amine addition reaction; subjecting theresulting reaction product and benzyne to Diels-Alder reaction and,optionally, to a reaction for modifying substituents born by benzyne;and, optionally, subjecting the resulting reaction product to an alkalitreatment and an acid treatment to obtain a polymerizable triptycenederivative of general formula (1) in which at least one of X or Y is asubstituent represented by the general formula (4).

One embodiment of the production method of a polymerizable triptycenederivative of the general formula (1) includes, but not limited to, amethod including: subjecting 9-halogen anthracene or 9,10-dihalogenanthracene and an acetal compound having a vinyl group to Heck couplingreaction and hydrolysis; subjecting the resulting reaction product andbenzyne to Diels-Alder reaction; and subjecting reaction withmethacryloly chloride to obtain a polymerizable triptycene derivative ofthe general formula (1) in which at least one of X or Y is a substituentrepresented by the general formula (5).

Also, a polymerizable triptycene derivative of the general formula (1)in which both X and Y are substituents represented by the generalformula (2); a polymerizable triptycene derivative of the generalformula (1) in which one of X and Y is a substituent represented by thegeneral formula (2) and the other of X and Y is a substituentrepresented by the general formula (3); a polymerizable triptycenederivative of the general formula (1) in which one of X and Y is asubstituent represented by the general formula (2) and the other of Xand Y is a substituent represented by the general formula (4); or apolymerizable triptycene derivative of the general formula (1) in whichone of X and Y is a substituent represented by the general formula (2)and the other of X and Y is a substituent represented by the generalformula (5); can be obtained by combining the above-described twoembodiments of the production method of a polymerizable triptycenederivative of the above general formula (1).

The polymer compound in one embodiment of the present invention may beformed by subjecting one or combination of two or more ofabove-mentioned polymerizable triptycene derivatives of the generalformula (1) and a compound capable of copolymerizing with thederivatives to a copolymerization reaction.

The preferable amount of the polymerizable triptycene derivative of thegeneral formula (1) in the polymer compound in one embodiment of thepresent invention is not particularly limited, but is, for example, 0.1wt % to 25 wt % relative to the total amount of the polymer compound,preferably 0.5 wt % to 20 wt %, more preferably 1 wt % to 15 wt %. Whenthe amount of the polymerizable triptycene derivative of the generalformula (1) is less than 0.1 wt %, the effect of the triptycenestructure is less likely to be exhibited in the obtained polymercompound. When the amount of the polymerizable triptycene derivative ofthe general formula (1) exceeds 25 wt %, it is undesirable because theobtained polymer compound is prone to cloudiness and loss of strength.

The compound capable of copolymerizing with the polymerizable triptycenederivative of the general formula (1) in the polymer compound in oneembodiment of the present invention is not particularly limited as longas it can be a monomer component as is generally known, but for example,a hydrophilic compound is preferably used. In the resulting polymercompound obtained by using the hydrophilic compound, each of the threebenzene rings in the triptycene structure can rotate evenly about theaxis formed by barrelene and the introduced polymerizable functionalgroups are hydrophilic groups. Thus, the polymer compound canencapsulate a hydrophilic material or a hydrophobic material and it ispossible to control the rate and the extent of diffusion of theencapsulated material when it is released from the polymer compound. Thepolymer compound with such characteristics can be used in a variety ofapplications, including, for example, liquid crystal alignment film,liquid crystal display elements, organic EL displays, organic thin filmswith electron transporting properties, light-emitting elements andorganic conductive compositions, as well as hydrogels, medical devices,ophthalmic lenses and DDS devices.

The hydrophilic compound capable of copolymerizing with thepolymerizable triptycene derivative of the general formula (1) is notparticularly limited as long as it can be a hydrophilic monomercomponent as is generally known, and examples thereof include(meth)acrylic monomers such as N, N-dimethylacrylamide, 2-hydroxyethylmethacrylate, (meth)acrylic acid, polyethylene glycol monomethacrylate,and glycerol methacrylate; and vinyl monomers such as N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide,N-vinyl-N-ethylformamide, and N-vinylformamide, and one or two or moreof these can be used alone or in combination. The amount of thehydrophilic compound capable of copolymerizing with the polymerizabletriptycene derivative of the general formula (1) is not particularlylimited, but is, for example, 75 wt % to 99.9 wt % relative to the totalamount of the polymer compound, preferably 80 wt % to 99.5 wt %, andmore preferably 75 wt % to 99 wt %. Depending on the type and amount ofhydrophilic compound capable of copolymerizing with the polymerizabletriptycene derivative of the general formula (1), it is possible toobtain the polymer compound with the desired flexibility and watercontent.

In order to impart strength, shape stability and flexibility to thepolymer compound in one embodiment of the present invention, it can beused linear, branched-chain or cyclic alkyl(meth)acrylates such asmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate,i-propyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate,t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,cyclohexyl(meth)acrylate, methoxydiethyleneglycol(meth)acrylate,ethoxydiethyleneglycol(meth)acrylate, phenyl(meth)acrylate,phenoxyethyl(meth)acrylate, benzyl(meth)acrylate, isobonyl(meth)acrylateas a hydrophobic compound capable of copolymerizing with thepolymerizable triptycene derivative of the general formula (1).According to desired physical properties, one or two or more of thehydrophobic compounds can be appropriately blended alone or incombination. The amount of the hydrophobic compound capable ofcopolymerizing with the polymerizable triptycene derivative of thegeneral formula (1) is not particularly limited, but is, for example, 0wt % to 30 wt % relative to the total amount of the polymer compound,and preferably 0 wt % to 20 wt %. When the amount of the hydrophobiccompound capable of copolymerizing with the polymerizable triptycenederivative of the general formula (1) exceeds 30 wt %, the strength,shape stability, or flexibility of the obtained polymer compound may bereduced.

In order to impart heat resistance and mechanical properties to thepolymer compound in one embodiment of the present invention,cross-linkable compounds such as a (meth)acrylate-based cross-linkablecompound and a vinyl-based cross-linkable compound can be used as aconstituent. Examples of the (meth)acrylate-based cross-linkablecompound include ethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycoldi(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropantri(meth)acrylate, pentaerythritol tri(meth)acrylate. Examples ofthe vinyl-based cross-linkable compound include allyl (meth)acrylate,diaryl maleate, diaryl fumarate, diaryl succinate, diaryl phthalate,triaryl cyanurate, triaryl isocyanurate, diethylene glycol bis-allylcarbonate, triaryl phosphate, triaryl trimethylate, diaryl ether, N,N-diaryl melamine, divinylbenzene. According to desired physicalproperties, one or two or more of the cross-linkable compounds can beappropriately blended alone or in combination. The amount of thecross-linkable compound is not particularly limited, but is, forexample, 0.01 wt % to 10 wt % relative to the total amount of thepolymer compound, and preferably 0.05 wt % to 3 wt %. When the amount ofthe cross-linkable compound exceeds 10 wt %, the flexibility of theobtained polymer compound may be reduced.

The polymer compound in one embodiment of the present invention can beproduced by combining steps known to those skilled in the art, and theproduction method is not particularly limited, but can include, forexample, the following steps; a step of obtaining a monomer mixture byadding a polymerization initiator to a mixture of monomer compounds suchas the polymerizable triptycene derivative of the general formula (1)which is a as constituent component, the hydrophilic compound capable ofcopolymerizing with the polymerizable triptycene derivative of thegeneral formula (1), the hydrophobic compound capable of copolymerizingwith the polymerizable triptycene derivative of the general formula (1)and the cross-linkable compound, stirring and dissolving; and a step ofputting the resulting monomer mixture into the desired molding mold andobtaining a copolymer by a copolymer reaction; a step of obtaining apolymer compound as a hydrogel by hydrating and swelling the moldedcopolymer after cooling, peeling the copolymer from the molding mold,and cutting and, optionally polishing.

Examples of the polymerization initiator include peroxide polymerizationinitiators such as lauroyl peroxide, cumene hydroperoxide and benzoylperoxide, which are general radical polymerization initiators; azopolymerization initiators such as azobis dimethylvaleronitrile andazobis isobutyronitrile (AIBN). One or two or more of the polymerizationinitiators can be used alone or in combination. The addition amount ofthe polymerization initiator is not particularly limited as long as itis sufficient to promote the copolymerization reaction of the monomer,for example, 10 ppm to 7000 ppm relative to the total monomer weight ofthe polymerization component is preferable.

The step of obtaining the copolymer can be carried out by putting themonomer mixture into a molding mold of metal, glass, plastic and thelike, sealing, raising the temperature in the range of 25° C. to 120° C.in a stepwise or continuous manner in a thermostatic oven, andcompleting the polymerization in 5 hours to 120 hours. Ultraviolet rays,electron beams, gamma rays and the like can be used for thepolymerization. In addition, a solution polymerization can be applied byadding water or an organic solvent to the monomer mixture.

In the step of obtaining the hydrogel, the polymer is cooled to roomtemperature after the polymerization is completed, the resulting polymeris peeled off from the molding mold, and after cutting and polishing asnecessary, the hydrogel is hydrated and swollen to become hydrogel.Examples of the liquid (swelling liquid) used include water,physiological saline, isotonic buffer. The swelling liquid is heated to60° C.-100° C. and soaked for a certain period of time to achieve aswollen state. In addition, it is preferable to remove the unpolymerizedmonomer contained in the polymer at the time of swelling treatment.

The present invention will now be described more specifically withreference to the following Examples, which are not intended to limit thepresent invention. The present invention may take various forms to theextent that the objectives of the present invention are achieved.

EXAMPLES Example 1. Synthesis of Triptycene Derivative (6)

1. Synthesis Scheme for Triptycene Derivative (6)

A triptycene derivative (6) was synthesized according to the followingScheme (I):

2. Synthesis of Compound (b)

Compound (b) in Scheme (I) was synthesized according to a methoddescribed in Ke Pan, et al., Journal of Organometallic Chemistry, 2008;693(17); p. 2863-2868, the disclosure of which is incorporated herein byreference in its entirety. Specifically, to a dimethylformamide solution(30 ml) of 2.7 g (10 mmol) of compound (a), which is 9-bromoanthracene,0.19 g (0.2 mmol) of Herrmann's palladacycle, 2.1 g (15 mmol) ofpotassium carbonate, and 2.3 mL (15 mmol) of acrolein diethyl acetalwere added under an argon atmosphere at room temperature and the mixturewas stirred overnight at 110° C. to allow the reaction to proceed. Theresulting reaction mixture was allowed to cool to room temperature anddiluted with ethyl acetate. This was followed by washing with 1Nhydrochloric acid, a saturated aqueous sodium bicarbonate solution and asaturated brine. The separated organic layer was dried over anhydrousmagnesium sulfate and the solvent was removed by evaporation. Theresulting residue was purified by silica gel column chromatography toobtain 2.4 g (87% yield) of compound (b).

3. Synthesis of Compound (c)

To a solution of 0.87 g (3.1 mmol) of compound (b) dissolved in 15 mlacetonitrile, 0.57 g (3.7 mmol) of cesium fluoride and 0.91 mL (3.7mmol) of 2-(trimethylsilyl)phenyl trifrate were added under an argonatmosphere and the mixture was stirred at 40° C. for 18 hours. Afterstirring, the reaction mixture was allowed to cool to room temperatureand filtrated through Celite. The resulting filtrate was concentratedunder reduced pressure. The resulting residue was purified by silica gelcolumn chromatography to obtain 0.92 g (83% yield) of compound (c).

NMR spectra for the resulting compound (c) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.35 (t, 3H), 3.17 (m, 2H), 3.35 (m, 2H), 4.31 (q,2H), 5.35 (s, 1H), 7.00 (m, 6H), 7.37 (m, 6H)

¹³C-NMR (CDCl₃) δ ppm; 14.47, 22.61, 30.96, 53.48, 54.58, 61.01, 122.12,123.70, 125.02, 125.14, 145.76, 146.99, 174.20

4. Synthesis of Compound (d)

0.20 g (5.3 mmol) of lithium aluminum hydride was dissolved in 15 mLtetrahydrofuran chilled to 0° C. under an argon atmosphere to form asolution. To the resulting solution, 1.56 g (4.4 mmol) of compound (c)was added and the mixture was stirred for three hours at roomtemperature. While the resulting reaction mixture was chilled on ice,0.2 mL water, a 0.2 mL 15 w/v % aqueous sodium hydroxide solution, and0.6 mL water were sequentially added dropwise slowly and the mixture wasstirred for one hour at room temperature. After stirring, the reactionmixture was filtrated through Celite. The resulting filtrate wasconcentrated under reduced pressure. The resulting residue was purifiedby silica gel column chromatography to obtain 1.34 g (98% yield) ofcompound (d).

NMR spectra for the resulting compound (d) were as follows:

¹H-NMR (CDCl₃) δ ppm; 2.41 (m, 2H), 2.98 (m, 2H), 4.00 (t, 2H), 5.34 (s,1H), 6.96 (m, 6H), 7.36 (m, 6H).

¹³C-NMR (CDCl₃) δ ppm; 24.36, 28.23, 53.29, 54.63, 64.00, 122.44,123.60, 124.88, 124.98, 146.33, 147.07.

5. Synthesis of Triptycene Derivative (6)

To a solution of 1.34 g (4.3 mmol) of compound (d) dissolved in 20 mLtetrahydrofuran, 0.90 mL (6.5 mmol) triethylamine and 0.61 mL (6.5 mmol)methacryloyl chloride were added under an argon atmosphere at 0° C. andthe mixture was stirred at 0° C. for 18 hours. After stirring, thereaction was quenched by adding a saturated aqueous sodium bicarbonatesolution and the organic compound in the solution was extracted withdiethyl ether. The extracted organic layer was washed with saturatedbrine and dried with anhydrous magnesium sulfate. The solvent was thenremoved from the dried organic layer by evaporation and the resultingresidue was purified by silica gel column chromatography to obtain 1.03g (63% yield) of a triptycene derivative (6).

NMR spectra for the resulting triptycene derivative (6) were as follows:

¹H-NMR (CDCl₃) δ ppm; 2.04 (s, 3H), 2.60 (m, 2H), 3.04 (m, 2H), 4.58 (t,2H), 5.36 (s, 1H), 5.63 (m, 1H), 6.25 (s, 1H), 6.99 (m, 6H), 7.39 (m,6H).

¹³C-NMR (CDCl₃) δ ppm; 18.60, 24.53, 24.57, 53.15, 54.62, 65.64, 122.28,123.68, 124.91, 125.07, 125.85, 136.50, 146.09, 147.04, 167.77.

Example 2. Synthesis of Triptycene Derivative (7)

1. Synthesis Scheme for Triptycene Derivative (7)

A triptycene derivative (7) was synthesized according to the followingScheme (II):

2. Synthesis of Compound (b)

Compound (b) was synthesized with reference to “2. Synthesis of compound(b)” in Example 1.

3. Synthesis of Compound (e)

To a solution of 1.1 g (10 mmol) of benzoquinone dissolved in 15 mLdichrolomethane, 1.1 mL (9.0 mmol) of a boron trifluoride-diethyl ethercomplex was added under an argon atmosphere at 0° C. and the mixture wasstirred for 30 min. After stirring, the reaction mixture was cooled to−20° C. To the cooled reaction mixture, 0.56 g (2.0 mmol) of compound(b) was added and the mixture was stirred for three hours at −20° C.After stirring, the reaction mixture was allowed to cool to roomtemperature and washed with saturated brine. The organic layer separatedfrom the washed reaction mixture was then dried over anhydrous magnesiumsulfate. The solvent was removed from the dried organic layer byevaporation and the resulting residue was purified by silica gel columnchromatography to obtain 0.67 g (87% yield) of compound (e).

NMR spectra for the resulting compound (e) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.37 (t, 3H), 2.80 (m, 2H), 2.90 (m, 1H), 2.99 (d,1H), 3.22 (dd, 1H), 3.34 (m, 1H), 4.29 (dd, 2H), 4.65 (d, 1H), 6.12 (d,2H), 7.18 (m, 6H), 7.41 (m, 2H).

¹³C-NMR (CDCl₃) δ ppm; 14.48, 24.00, 30.22, 49.38, 50.10, 51.05, 60.86,122.24, 123.17, 124.20, 124.93, 126.63, 126.73, 126.85, 127.06, 139.03,140.05, 141.37, 141.88, 142.98, 173.85, 197.73, 198.89.

4. Synthesis of Compound (f)

To a solution of 0.93 g (2.4 mmol) of compound (e) dissolved in 10 mLdimethylformamide, 2.0 g (6.0 mmol) of cesium carbonate and 0.67 mL (7.2mmol) methyl iodide were added under an argon atmosphere and the mixturewas stirred at 40° C. for 18 hours. After stirring, the reaction mixturewas filtrated through Celite. The resulting filtrate was concentratedunder reduced pressure and the resulting concentrated residue waspurified by silica gel column chromatography to obtain 0.82 g (82%yield) of compound (f).

NMR spectra for the resulting compound (f) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.37 (t, 3H), 3.09 (br s, 2H), 3.66 (s, 3H), 3.74(br s, 2H), 3.80 (s, 3H), 4.29 (q, 2H), 5.86 (s, 1H), 6.51 (m, 2H), 7.01(m, 4H), 7.43 (m, 4H).

¹³C-NMR (CDCl₃) δ ppm; 14.52, 24.23, 32.65, 32.71, 47.27, 56.08, 56.50,60.47, 109.73, 110.23, 123.47, 123.79, 124.78, 125.21, 125.55, 146.50,148.86, 150.17, 174.92.

5. Synthesis of Compound (g)

The same procedure was followed as in “4. Synthesis of compound (d)” inExample 1, except that 0.69 g (1.7 mmol) of compound (f) was used inplace of compound (c) to obtain 0.58 g (93% yield) of compound (g).

NMR spectra for the resulting compound (g) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.65 (br s, 1H), 2.34 (br s, 2H), 3.28 (br s, 2H),3.70 (s, 3H), 3.79 (s, 3H), 4.05 (t, 2H), 5.85 (s, 1H), 6.50 (m, 2H),7.01 (m, 4H), 7.46 (m, 4H).

¹³C-NMR (CDCl₃) δ ppm; 26.06, 29.85, 29.99, 47.38, 56.56, 56.60, 64.70,109.68, 110.72, 123.76, 124.66, 124.91, 146.67, 148.94, 150.45.

6. Synthesis of Triptycene Derivative (7)

The same procedure was followed as in “5. Synthesis of triptycenederivative (6)” in Example 1, except that 0.58 g (1.6 mmol) of compound(g) was used in place of compound (d) to obtain 0.62 g (90% yield) oftriptycene derivative (7).

NMR spectra for the resulting triptycene derivative (7) were as follows.

¹H-NMR (CDCl₃) δ ppm; 2.04 (m, 3H), 2.47 (br s, 2H), 3.33 (br s, 2H),3.70 (s, 3H), 3.78 (s, 3H), 4.54 (t, 2H), 5.62 (m, 1H), 5.86 (s, 1H),6.23 (d, 1H), 6.50 (br s, 2H), 7.02 (m, 4H), 7.41 (br s, 2H), 7.50 (brs, 2H).

¹³C-NMR (CDCl₃) δ ppm; 18.59, 25.91, 26.30, 47.35, 54.86, 56.32, 56.54,660.33, 109.66, 110.47, 123.78, 124.66, 124.96, 125.54, 136.70, 138.11,146.66, 148.88, 150.37, 167.87.

Example 3. Synthesis of Triptycene Derivative (8)

1. Synthesis Scheme for Triptycene Derivative (8)

A triptycene derivative (8) was synthesized according to the followingScheme (III):

2. Synthesis of Compound (b)

Compound (b) was synthesized with reference to “2. Synthesis of compound(b)” in Example 1.

3. Synthesis of Compound (e)

Compound (e) was synthesized with reference to “3. Synthesis of compound(e)” in Example 2.

4. Synthesis of Compound (h)

To a solution of 0.50 g (1.3 mmol) of compound (e) dissolved in 10 mLdimethylformamide, 1.1 g (3.2 mmol) of cesium carbonate and 0.37 mL (3.9mmol) of 2-methoxyethyl bromide were added under an argon atmosphere andthe mixture was stirred at 40° C. for 18 hours. After stirring, thereaction mixture was filtrated through Celite. The resulting filtratewas concentrated under reduced pressure and the resulting concentratedresidue was purified by silica gel column chromatography to obtain 0.57g (87% yield) of compound (h).

NMR spectra for the resulting compound (h) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.29 (t, 3H), 2.98 (m, 2H), 3.38 (br s, 3H), 3.45(s, 3H), 3.70 (m, 6H), 3.92 (m, 2H), 4.00 (m, 2H), 4.22 (q, 2H), 5.81(s, 1H), 6.44 (s, 2H), 6.94 (m, 4H), 7.38 (m, 4H).

¹³C-NMR (CDCl₃) δ ppm; 14.55, 24.37, 32.09, 47.45, 59.20, 59.41, 60.55,69.25, 69.89, 71.22, 71.39, 112.36, 123.56, 123.89, 124.80, 125.18,146.40, 148.25, 149.90, 174.92.

5. Synthesis of Compound (i)

Compound (i) 0.41 g (97% yield) was obtained with reference to “4.Synthesis of compound (d)” in Example 1, except that 0.46 g (0.92 mmol)of compound (h) was used in place of compound (c).

NMR spectra for the resulting compound (i) were as follows:

¹H-NMR (CDCl₃) δ ppm; 2.36 (br s, 2H), 3.46 (br s, 2H), 3.47 (s, 3H),3.52 (s, 3H), 3.76 (dd, 4H), 4.03 (m, 4H), 5.88 (s, 1H), 6.46 (d, 1H),6.52 (d, 1H), 7.00 (m, 4H), 7.40 (d, 2H), 7.51 (d, 2H).

¹³C-NMR (CDCl₃) δ ppm; 26.44, 29.14, 47.54, 58.85, 59.41, 64.48, 68.92,69.89, 71.39, 71.69, 112.39, 123.81, 124.66, 124.93, 146.46, 148.42,149.88.

6. Synthesis of Triptycene Derivative (8)

The same procedure was followed as in “5. Synthesis of triptycenederivative (6)” in Example 1, except that 0.71 g (1.5 mmol) of compound(i) was used in place of compound (d) to obtain 0.63 g (77% yield) oftriptycene derivative (8).

NMR spectra for the resulting triptycene derivative (8) were as follows.

¹H-NMR (CDCl₃) δ ppm; 2.04 (m, 3H), 2.51 (br s, 2H), 3.44 (m, 5H), 3.52(s, 3H), 3.71 (t, 2H), 3.77 (m, 2H), 3.97 (m, 2H), 4.06 (m, 2H), 4.53(t, 2H), 5.62 (m, 1H), 5.88 (s, 1H), 6.24 (m, 1H), 6.51 (m, 2H), 7.03(m, 4H), 7.41 (m, 2H), 7.53 (br s, 2H).

¹³C-NMR (CDCl₃) δ ppm; 14.26, 18.61, 22.78, 25.43, 26.16, 31.71, 47.53,59.39, 66.22, 69.92, 71.39, 112.34, 112.44, 123.87, 124.64, 124.98,125.58, 136.67, 146.51, 148.24, 150.02, 167.87.

Example 4. Synthesis of Triptycene Derivatives (9) and (10)

1. Synthesis Scheme for Triptycene Derivatives (9) and (10)

Triptycene derivatives (9) and (10) were synthesized according to thefollowing Scheme (IV):

2. Synthesis of Compound (k)

Compound (k) was obtained with reference to “2. Synthesis of compound(b)” in Example 1, except that compound (j) was used in place ofcompound (a).

NMR spectra for the resulting compound (k) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.28 (t, 6H), (2.78 (m, 4H), 3.97 (m, 4H), 4.21(q, 4H), 7.55 (dd, 4H), 8.33 (dd, 4H).

¹³C-NMR (CDCl₃) δ ppm; 14.38, 23.60, 35.53, 60.81, 124.95, 125.63,129.47, 132.03, 173.22.

3. Synthesis of Compound (1)

To a solution of 0.26 g (0.69 mmol) of compound (k) dissolved in 10 mLacetonitrile, 0.13 g (0.83 mmol) of cesium fluoride and 0.20 mL (0.83mmol) of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate were addedunder an argon atmosphere and the mixture was stirred at 40° C. for 18hours. After stirring, the reaction mixture was filtrated throughCelite. The resulting filtrate was concentrated under reduced pressureand the resulting concentrated residue was purified by silica gel columnchromatography to obtain 0.29 g (93% yield) of compound (l).

NMR spectra for the resulting compound (l) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.36 (m, 6H), 3.16 (m, 4H), 3.34 (m, 4H), 4.33 (q,4H), 7.02 (m, 6H) 7.40 (m, 6H).

¹³C-NMR (CDCl₃) δ ppm; 14.47, 22.75, 31.03, 52.76, 61.04, 122.19,124.88, 146.91, 174.18.

4. Synthesis of Compound (m)

Compound (m) 0.34 g (93% yield) was obtained with reference to “4.Synthesis of compound (d)” in Example 1, except that 0.45 g (1.0 mmol)of compound (l) was used in place of compound (c).

NMR spectra for the resulting compound (m) were as follows:

¹H-NMR (CDCl₃) δ ppm; 2.49 (m, 4H), 3.00 (m, 4H), 4.13 (m, 4H), 7.00 (brs, 6H), 7.43 (br s, 6H).

¹³C-NMR (CDCl₃) δ ppm; 24.59, 28.37, 52.50, 64.16, 122.29, 124.63.

5. Synthesis of Triptycene Derivative (9)

To a solution of 50 mg (0.14 mmol) of compound (m) dissolved in 5 mLtetrahydrofuran, 5.4 mg (0.14 mmol) of sodium hydride was added under anargon atmosphere at 0° C. and the mixture was stirred at 0° C. for 30minutes. Methacryloyl chloride 12 μL (0.13 mmol) was added to themixture and the mixture was stirred at 0° C. for 18 hours. Afterstirring, the reaction was quenched by adding a saturated aqueous sodiumbicarbonate solution and the organic compound in the solution wasextracted with diethyl ether. The extracted organic layer was washedwith saturated brine and dried with anhydrous magnesium sulfate. Thesolvent was then removed from the dried organic layer by evaporation andthe resulting residue was purified by silica gel column chromatographyto obtain 38 mg (64% yield) of a triptycene derivative (9).

NMR spectra for the resulting compound (9) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.62 (br s, 1H), 2.05 (s, 3H), 2.47 (m, 2H), 2.61(m, 2H), 3.01 (dd, 4H), 4.13 (t, 2H), 4.59 (t, 2H), 5.63 (s, 1H), 6.25(s, 1H), 7.01 (s, 6H), 7.43 (br s, 6H).

¹³C-NMR (CDCl₃) δ ppm; 18.57, 24.60, 24.78, 28.34, 52.38, 52.52, 61.57,61.14, 65.70, 122.34, 124.78, 125.94, 167.94.

6. Synthesis of Triptycene Derivative (10)

Jones reagent was dropped into a solution of 27 mg (0.06 mmol) oftriptycene derivative (9) dissolved 1 mL acetone at 0° C. until thesolution turned orange. After the solution was stirred for 10 minutes,and the resulting organic material was extracted with diethyl etherthree times. The extracted organic layer was washed with saturated brineand dried with anhydrous magnesium sulfate. The solvent was then removedfrom the dried organic layer by evaporation and the resulting residuewas purified by silica gel column chromatography to obtain 9.9 mg (36%yield) of a triptycene derivative (10).

NMR spectra for the resulting triptycene derivative (10) were asfollows:

¹H-NMR (CDCl₃) δ ppm; 2.04 (m, 3H), 2.62 (m, 2H), 3.04 (m, 2H), 3.30 (d,2H), 3.38 (d, 2H), 4.60 (t, 2H), 5.65 (s, 1H), 6.26 (s, 1H), 7.05 (br s,6H), 7.42 (br s, 6H).

¹³C-NMR (CDCl₃) δ ppm; 18.57, 22.59, 24.58, 30.60, 52.44, 65.67, 122.09,124.98, 125.98, 135.60, 147.31, 150.29, 158.26, 160.24, 167.96.

Example 5. Synthesis of Triptycene Derivative (11)

1. Synthesis Scheme for Triptycene Derivative (11)

A triptycene derivative (11) was synthesized according to the followingScheme (V):

2. Synthesis of Compound (b)

Compound (b) was synthesized with reference to “2. Synthesis of compound(b)” in Example 1.

3. Synthesis of Compound (n)

To 5 mL of dimethylformamide, 0.94 mL (10.1 mmol) of phosphoryl chloridewas added dropwise under an argon atmosphere at 0° C. and the mixturewas stirred at room temperature for 1.5 hours. To the stirred reactionmixture, 1.0 g (3.6 mmol) of compound (b) was dissolved and the mixturewas stirred at 110° C. for 18 hours. After stirring, the reactionmixture was allowed to cool to room temperature and diluted with ethylacetate. The diluted reaction mixture was sequentially washed with 1Nhydrochloric acid, a saturated aqueous sodium bicarbonate solution and asaturated brine. The organic layer separated after washing was driedover anhydrous magnesium sulfate. The solvent was removed from the driedorganic layer by evaporation and the resulting residue was purified bysilica gel column chromatography to obtain 0.78 g (71% yield) ofcompound (n).

NMR spectra for the resulting compound (n) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.25 (m, 3H), 2.77 (m, 2H), 3.98 (m, 2H), 4.20 (q,2H), 7.62 (m, 4H), 8.33 (m, 2H), 8.92 (dd, 2H), 11.45 (s, 1H).

¹³C-NMR (CDCl₃) δ ppm; 14.34, 24.19, 35.32, 60.99, 124.45, 124.77,125.01, 126.30, 128.48, 129.08, 131.64, 141.68, 172.65, 193.63.

4. Synthesis of Compound (o)

To a solution dissolved 0.74 g (2.4 mmol) of compound (n) in 10 mL ofacetonitrile, 1.1 g (7.2 mmol) of benzyl carbamate, 0.59 mL (7.2 mmol)of triethylsilane and 0.61 mL (7.0 mmol) of trifluoroacetic acid wereadded dropwise under an argon atmosphere and the mixture was stirred atroom temperature for 18 hours. After stirring, the reaction mixture wasdiluted with ethyl acetate. The diluted reaction mixture wassequentially washed with a saturated sodium hydrogen carbonate solutionand a saturated saline. The organic layer separated after washing wasdried over anhydrous magnesium sulfate. The solvent was removed from thedried organic layer by evaporation and the resulting residue waspurified by silica gel column chromatography to obtain 0.84 g (83%yield) of compound (o).

NMR spectra for the resulting compound (o) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.21 (m, 3H), 2.69 (m, 2H), 3.90 (m, 2H), 4.13 (q,2H), 4.94 (s, 1H), 5.08 (s, 2H), 5.32 (d, 2H), 7.28 (m, 5H), 7.50 (m,4H), 8.27 (m, 4H).

¹³C-NMR (CDCl₃) δ ppm; 14.36, 23.60, 35.40, 37.73, 60.84, 67.00, 124.84,125.82, 126.36, 128.16, 128.60, 129.38, 130.19, 134.17, 136.52, 156.23,173.02.

5. Synthesis of compound (p) The same procedure was followed as in “3.Synthesis of compound (c)” in Example 1, except that 0.29 g (0.66 mmol)of compound (o) used in place of compound (b) to obtain 0.27 g (78%yield) of compound (p).

NMR spectra for the resulting compound (p) were as follows:

¹H-NMR (CDCl₃) δ ppm; 1.36 (m, 3H), 3.14 (m, 2H), 3.34 (m, 2H), 4.33 (q,2H), 4.85 (d, 2H), 5.26 (s, 2H), 5.42 (m, 1H), 7.03 (m, 6H), 7.35 (m,11H).

¹³C-NMR (CDCl₃) δ ppm; 14.48, 22.68, 30.97, 40.20, 52.03, 52.92, 61.11,67.19, 122.35, 125.26, 128.20, 128.33, 128.69, 136.58, 147.07, 165.9,174.08.

6. Synthesis of Compound (q)

The same procedure was followed as in “4. Synthesis of compound (d)” inExample 1, except that 0.15 g (0.29 mmol) of compound (p) used in placeof compound (c) to obtain 87 mg (88% yield) of compound (q).

NMR spectra for the resulting compound (q) were as follows:

¹H-NMR (CDCl₃) δ ppm; 2.45 (m, 2H), 3.03 (m, 2H), 4.11 (d, 2H), 4.91 (d,2H), 6.29 (s, 1H), 7.02 (br s, 6H), 7.39 (m, 6H), 8.41 (s, 1H).

¹³C-NMR (CDCl₃) δ ppm; 24.47, 28.19, 37.44, 51.49, 52.71, 63.89, 121.92,125.10, 161.69.

7. Synthesis of Triptycene Derivative (11)

To a solution of 25 mg (0.073 mmol) of compound (q) dissolved in 1 mLdichloromethane, 22 mg (0.080 mmol) of 1-[2-(trimethylsilyl)ethoxycarbonyloxy] benzotriazole was added under an argon atmosphere andthe mixture was stirred at room temperature for 30 minutes. The reactionwas quenched by adding 5% aqueous sodium bicarbonate solution and theorganic compound in the solution was extracted with dichloromethane. Theextracted organic layer was washed with 5% aqueous sodium bicarbonatesolution and dried with anhydrous magnesium sulfate. Compound (r) wasobtained by removing the solvent from the dried organic layer. To asolution of resulting compound (r) dissolved in 5 mL tetrahydrofuran, 20μL (0.14 mmol) of triethylamine and 14 μL (0.14 mmol) of methacryloylchloride were added under an argon atmosphere and the mixture wasstirred at 0° C. for 18 hours. After stirring, the reaction was quenchedby adding a saturated aqueous sodium bicarbonate solution and theorganic compound in the solution was extracted with diethyl ether. Theextracted organic layer was washed with saturated brine and dried withanhydrous magnesium sulfate. The solvent was then removed from the driedorganic layer by evaporation and the resulting residue was purified bysilica gel column chromatography to obtain 6.5 mg (18% yield) of atriptycene derivative (11).

NMR spectra for the resulting triptycene derivative (11) were asfollows:

¹H-NMR (CDCl₃) δ ppm; 0.07 (s, 9H), 1.67 (m, 4H), 2.04 (s, 3H), 2.59 (m,2H), 3.05 (m, 2H), 4.60 (t, 2H), 4.93 (d, 2H), 5.65 (s, 1H), 6.25 (s,1H), 7.06 (m, 6H), 7.41 (m, 6H), 8.46 (s, 1H).

¹³C-NMR (CDCl₃) δ ppm; 0.06, 1.10, 18.57, 24.53, 31.04, 37.40, 51.56,52.61, 64.17, 65.55, 122.04, 125.30, 126.01, 136.57, 161.72, 167.90.

Example 6. Synthesis of Triptycene Derivative (12)

1. Synthesis Scheme for Triptycene Derivative (12)

A triptycene derivative (12) was synthesized according to the followingScheme (VI):

2. Synthesis of Compound (k)

Compound (k) was synthesized with reference to “2. Synthesis of compound(k)” in Example 4.

3. Synthesis of Compound (l)

Compound (l) was synthesized with reference to “3. Synthesis of compound(l)” in Example 4.

4. Synthesis of Compound (m)

Compound (m) was synthesized with reference to “4. Synthesis of compound(m)” in Example 4.

5. Synthesis of Triptycene Derivative (12)

To a solution of 35 mg (0.094 mmol) of compound (m) dissolved in 5 mLtetrahydrofuran, 33 μL (0.24 mmol) of triethylamine and 22 μL (0.24mmol) of methacryloyl chloride were added under an argon atmosphere at0° C. and the mixture was stirred at 0° C. for 18 hours. After stirring,the reaction was quenched by adding a saturated aqueous sodiumbicarbonate solution and the organic compound in the solution wasextracted with diethyl ether. The extracted organic layer was washedwith saturated brine and dried with anhydrous magnesium sulfate. Thesolvent was then removed from the dried organic layer by evaporation andthe resulting residue was purified by silica gel column chromatographyto obtain 26 mg (54% yield) of a triptycene derivative (12).

NMR spectra for the resulting triptycene derivative (12) were asfollows:

¹H-NMR (CDCl₃) δ ppm; 2.05 (d, 6H), 2.60 (m, 4H), 3.02 (m, 4H), 4.60 (t,4H), 5.64 (m, 2H), 6.25 (s, 2H), 7.02 (m, 6H), 7.43 (s, 6H).

¹³C-NMR (CDCl₃) δ ppm; 18.56, 24.57, 24.75, 52.39, 65.67, 122.41,124.80, 125.93, 136.60, 167.91.

Example 7. Formation of Polymer Hydrogel Containing TriptyceneDerivatives (9), (10), (11) and (12) Obtained by Examples 4-6

A monomer mixture was obtained by mixing 0.5 g of each of the triptycenederivative compounds (9)-(12) synthesized in Example 1, 9.5 g of2-hydroxyethyl methacrylate, 0.01 g of ethylene glycol dimethacrylate,and 2000 ppm of azobisisobutyronitrile (AIBN) at room temperature andstirring for about one hour with sufficient nitrogen substitution. Afterstirring, the monomer mixture was placed in a molding mold and heated to50° C.-100° C. for 25 hours to obtain the polymer. The resulting polymerwas cooled to reach a room temperature, released from the mold, andimmersed in distilled water at about 60° C. for about 4 hours to hydrateand swell to obtain triptycene derivative-containing hydrogel of fourtypes.

As a comparative example, the same procedure was followed as in Example4, except that compound 8 represented by following formula (A) in PatentDocument 9 (JP 2008-075407 A) was used in place of compounds (9)-(12) tomix 9.5 g of 2-hydroxyethyl methacrylate, 0.01 g of ethylene glycoldimethacrylate, and 2000 ppm of AIBN. However, a homogeneous solutioncould not be obtained and it could not be used for the copolymerizationreaction, when compound 8 of Patent Document 9 was used. This suggeststhat the conventional triptycene derivatives have low compatibility withhydrophilic compound.

INDUSTRIAL APPLICABILITY

The polymerizable triptycene derivative in one embodiment of the presentinvention and the polymer compound as constituent component thereof canbe used as materials in a variety of applications, including, forexample, liquid crystal alignment films, liquid crystal displayelements, organic EL displays, organic thin films with electrontransporting properties, light-emitting elements and organic conductivecompositions, as well as hydrogels, medical devices, ophthalmic lensesand DDS devices.

The invention claimed is:
 1. A polymer compound comprising asconstituent component: a polymerizable triptycene derivative representedby the following general formula (1), and

wherein R₁ to R₄ are each independently a substituent selected from thegroup consisting of hydrogen atom, alkyl group, cycloalkyl group,heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group,alkoxy group, alkylthio group, arylether group, arylthioether group,aryl group, heteroaryl group, halogen atom, carbonyl group, carboxylgroup, oxycarbonyl group, carbamoyl group, amino group, phosphineoxidegroup, and silyl group, with the proviso that adjacent substituents maytogether form a ring; one of X and Y is a substituent represented by thefollowing general formula (2):

wherein n is an integer of 1 to 5; and R₅ shows hydrogen atom or methylgroup and the other of X and Y is a substituent selected from the groupconsisting of the substituents represented by the general formula (2),hydrogen atom and halogen atom, and protected or unprotected hydroxylgroup, hydroxylalkyl group, carboxyl group, carboxylalkyl group, aminogroup, aminoalkyl group, aminocarbonyl group, aminocarbonylalkyl group,alkoxy group, alkoxyalkyl group, alkoxycarbonyl group,alkoxycarbonylalkyl group, formyl group, formylalkyl group, and alkylgroup a compound capable of copolymerizing with the polymerizabletriptycene derivative.
 2. The polymer compound according to claim 1,wherein the other of X and Y is a substituent selected from the groupconsisting of the substituents represented by the following generalformula (3):

wherein n is an integer of 1 to 5; and R₆ is a substituent selected fromthe group consisting of hydrogen atom and alkyl group having any one ofcarbons 1 to 30, the substituents represented by the following generalformula (4):—(CH₂)_(n)—NHR₇   (4) wherein n is an integer of 1 to 5; and R₇ is asubstituent selected from the group consisting of hydrogen atom and acarbamate protective group, and the substituents represented by thefollowing general formula (5):—(CH₂)_(n)—OH   (5) wherein n is an integer of 1 to
 5. 3. The polymercompound according to claim 1, wherein the compound capable ofcopolymerizing with the polymerizable triptycene derivative is ahydrophilic compound capable of copolymerizing with at least onepolymerizable triptycene derivative.